Coumarone-indene resins and process of making the same



, Patented June Q,-f19 25 UNITED STAT-Es (PATENT,QOFFICE.. Q

nann omroan mus, or rinmnnnrm, "rnnnsvnvanm, Assmno1a BY MESNEASSIGNMENTS, we run xorrnnscomranr, or rrrrrsnunen, rmmsYnvam, aconronanon or rmsYLvAH coUmnoNE-mnnnn nnsms snnrnoonss or name sum Illenrawing.

To all whom it may concern:

Be it known that I, HARRY Cmrroun I ful Improvenient in Coumarone-IndeneResins and Processes of Making the Same, and do hereb declare that thefollowing is a full, cear, and exact description thereof. Myjinventionrelates particularly to a process designed for obtaining resinoussubstances of an advantageous character and the product thereof. Theobject of my invention" is "to' which aromatic oils, especially those obtained as by-prodncts. in the destructive distillation of, coal, such ascrude solvent naph tha, maybe treated to obtain resinous sub& stances ofan advantageous character. v The object ofmy Invention is particus ladyto obtain such resinous'substanceshaving a lighter color and a greaterdegree 6 of hardness and transparency than substances'of asimilar-nature previously produced;

Heretofore resinous substances of a {similar nature have been producedwhich have "a dark color, ,a semi-transparent appearance and show atendency to soften at a slightly elevated temperatures. Man

of the resins having undesirable characteristics mentioned above areobtained. by the poly mcrization of coal tar distillation oils withsulphuric acid and such resins often show substantial sulphuricacid veryfrequently contain "sulphur gases or organic salts of sulphur. Furtherthese resins are not ,well ada d for makr varnishes since films made,ere of turn when submerged in water. Another 0 ject of my invention-isto tain resinous substances thatvirill overcome the objectionablefea'tures'above referred to.

- for example O a l fro Wide a process and the product thereo in,

rcentages of phenols when de- 'structively ietilled. Oils polymerizedwith vide -a. process and a product thereof in which tar oils may be'polymerized toobresidue is ascribed a neaa ned s urf-10 r017. Serial ind185,453.

For example, I may proceed-asfollows:

uantity of aromatic oils, as; e oils obtained as by roducts in thedestructive distillation 0 coal and containing hydrocarbons of thebenzene employ a.

Series and P ly the na htha v late nsisting of solvent and eavy naphthewhich distils over, mainly between} and 200 '0. The naphtha distillate,is

heated to a moderately elevated temperature' asflforexample 45 CL, andan amount a of aluminum chloride is added a from 0.25 w to 1.25% of theweight of the oil,' while the whole is being agitated. When the polluerizatio'n'is complete; as indicated e fall of the-temperature afterthe re 1' ,nse

thereof due'to the heat of the react1on, the aluminum chloride is washedoutwith wa, ter, the. product is neutralized: by the add tion of asuitable alkalinereagent, such for. example as sodium hydroxide, andthe'excess-of alkali is removed by treatment wlth hot water. Theresinous compound Js then obtained by distilling oil from 1t the unpolymerizedoil. 1 I

f desired, the above process ma be. modified so as to obtaina'resinstill hter in 7 color I) treatingthe oil prior to e addi tion 0 aluminum"chloride with a small amount wof sulphuric. acid; preferably an amountsof from 0.1% to 1.0% of the weight i of the oil. Theioil' is thendlfltlllfid and '5 the distillate 'washed with water l after which thealuminum chloride is added and p the processicontinued in the"annerfabove' described. The treatment 0 the 011 with sulfuric. acid ,as'outlined above does not polymerize the eoumarone or m lene substances ofthe oil, and in fact this iscarefull guarded against. The funct on ofthe", sulfiiuc acid is to remove the hqllid 1111:, Saturateddark-resimformmg hydrocarbons in the 'oil I) decomposltlon or polymemtion. The, ecomposedor polymerized-1msaturated h drocarbons are left assblack H residue in t efstill after distillation. undesirable, and istherefore dlscarded. a I

"-A still fuijther-improvement 1n the color a,

be obtaifled'b app y ng mu ata remov f the n ly, m6

resin of thecoumarone and indene groups and has the followingcharacteristics: acid number of 0.25 to 0.40, ea onification number 40to 6.0, iodine num r 5.0% to iodine per gram resin, ash content .05%-

2 water.

' lates recovered of the constituents com osmg 40 j as 1%eriziagreactions.

'It will be noted that the acid and saponification numbers of theimproved resin are very low which indicatesa high acid and alkalineresisting quality. The iodine number is very low and indicates alow ercentage of unsaturated hydrocarbons w ich makes possible a transparentresin and gives increased atmospheric resistance to the res in. Themelting point of the resin is exceedingly high which insures anexcellent drying quality, hardness and permanenc and partlcular adaptsthe resin for varnis manufacture. By maintaining the improved resin'freefrom sulphur diokideand ash the transparency of the resin is msured andits resistance to alkalies, acids and atmospheric conditions are greatlyimproved. The high percentage of distilby distillation of the improvedresin is a criterion of the stability the resin. The high percentage of'stillat'e obtained from the resin also indicates the low percentage offree carbon therein.

The light colored resin, produced b the above described process wh inthe istillate of solvent na htha is a prelim-- inary treatment withsulfuric acid, consists of practically-sure paraccumarone and itshomologues, E and para-indene (0 11,) the sulfuric acid treatmentserving to remove polymerized dicyclopentadignlei )(C,H,,),, andpolymerized styrolenc While in-the preferred process of obtainmg thelightest colored resin b preliminarily polymerizing the dark resinormingbodies an removing them preferably by distilla- .tion prior to thepolymerization of the coumarone and indene compounds, sulphuric acid andaluminum chloride, respectively, vc i I agents, other specific mightbe-Iem loyed or are preferably employed as the polymerizmg pplymerizingagents 1; e sulphuric acid or c or'ide be -employed in both distillateand 10% to 13% oil by distillation.

above in detail, I wish it to be understood that man changes may be madetherein without eparting from the spirit thereof.

I claim: 4

1. A process which comprises producing a a resinous material from anaromatic oil by decom' sing unsaturated hydrocarbons thereo withsulphuric acid, distilling, polymerizing the distillate therefrom withaluminum chloride, and distilling the polymerized product to removeunpolymerized oil.

3. process, which comprises producing a resinous material from anaromatic oil by deco sing unsaturated hydrocarbons thereo with sulphuricacid, distilling, polymerizing the distillate therefrom with alu minumchloride,.and distilling the polymerized product under a vacuum toremove unpolzmerized oil. l

a. process which comprises producing a resinous material from anaromatic oil by polymerizing the oil with aluminum chloride, removal ofthe aluminum chloride by washing, neutralization of the product with analkali, removal of the excess alkali by washing, and removal of theun'polymerizcd .5. A process which comprises producing a resinousmaterial from an aromatic oil by decom osing the unsaturatedhydrocarbonsthereo with concentrated sulfuric acid in an amount. not sufiicient toolymerize the oil, distilling, polymerizin t e resin-forming substancesin the distillate with aluminum-chloride, removing the aluminum chlorideby washing, neutralizing the product with an alkali, removin the excessalkali by washing and removing unpolymerized 011 by distillation.

6. A process of producing a resinous'material which comprises treating,with 0.1% of its weight of sulfuric acid, a naphtha distillate of coal'tar containing oils disfilling up to approximately 2 C. to convertunsaturated hydrocarbons into substances readily separable from the oilby distillation,-dist1lling the treated oil and subjecting thedistillate to the action of alumi num chloride to olymerizeresin-forming constituents of sait' d stillate.

7. A process which comprises producing a resinous material from anaphtha distillate containing oils distilling up to approximately 2000., by decomposing unsaturated h drocarbons thereof with sulphuric acid,

distilling and treating the distillate therefrom with aluminum chloride.

8 A process of producing a resinous materlal which comprises treating,with 0.1%

to 1.0% of its weight of sulfuric acid, a naphtha distillate 0distilling up to approximately 200" convert unsaturated hydrocarbonsinto substances readily separable from the oil by distillation,distilling the treated oil and subjccting the distillate to the;actionof aluminum chloride in an amount of from 0.25% to 1.25% of the weightof the distillate to polymerize resin-forming constituents of saiddistiilate.

9. A process which comprises eliminating at least a substantialproportion of the unsaturated hydrocarbons contained in a naphthadistillate of coal-tar containing oils distilling up to approximately200 C., and subjecting the distillate, from which unsaturatedhydrocarbons have been eliminated, to the action of aluminum chloride.

10. A process which comprises eliminating at least a substantialproportion of the unsaturated hydrocarbons contained in a. naphthadistillate of coal-tar containing oils distilling up to approximately200 C., subjecting' the distillate, from which unsaturated hvdrocarbonshave beeneliminated, to the action of aluminum chloride to polymerizeresin-forming constituents and separating the resinous product from theunpolymerized oil.

11. In the process of producing resin from a liquid containing not onlycompounds of the couniarone-indene group but also compounds capable ofresinous bodies when subjectedto the action of sulfuric acid, the stepswhich comprise treating the liquid with sulfuric acid of sufficientstrength to polymerize said dark-resinforming compounds withoutappreciable polymerization of the contained coumaroneindene compounds,and then separatin the letter from the resulting dark resinous bodies bydistillation.

12. In the rocess of producing resin from a naphtha istillate of coaltar containing not only compounds of the coumaroneindene group oiforming dark resinous bodies when subjected to the action of sulfuricacid, the steps which comprise treating said distillate with sulfuricacid of suflicient strength'to polymerize said (lark-resin-formin;compounds without appreciable polymerization oi. the containedcoumaroue-indenc com pounds. and then separating the latter from theresulting dark resinous bodies by distillation.

13. That step in the process of producing resin from a liquid containingcompounds of the coumarone-indene group, which consists in initiallytreating the mixture with sulfuric acid of suilicient strength topolymerize dark resin-forming bodies without appreciable polymerizationof the contained coumarone-indene compounds, and separatcoal tarcontaininrr oils-'- to forming dark which 11 but also compounds capablegrou p together polymerized dark resin-forming bodies from theunpolymerized coumarone indene compounds.

14. That step in the operation of producing resin from crude solventnaphtha, which consists in initially treating the crude solvent naphthawit sulfuric acid of sulficient" strength to polymerize the containeddark resin-forming bodies without ap reciably polymerizing the containedlight resin-forming compounds, and separating the thus pol merized darkresin-forming bodies from the naphtha containing the unpolymerized lightresin-forming compounds.

15., s a new article of manufacture, a light colored resin consisting ofpractically pure paracoumaroneand its homologues, (C H O), and paraindene (C,,H,) being practically free from polymerized dicyclopentadiene(C H L, and polymerized st rolene (C H,),,

16. process which comprises producing ing the thus a resinous materialfrom an aromatic oildecomposing unsaturated hydrocarbons with sulphuricacid, distilling, and

thereof treating the distillate therefrom with aluminum chloride in anamount of from 0.25% to 1.25% of the weight of the oil.

17. A resinous polymerization product of the coumarone group having anacid numher loss than 0.5, a saponification number less than 7.0. aniodine number less than 207}, the melting oint higher than C'., andcharacterized y its products of destructive distillation being free fromphenols, sulphur dioxide and organic sulphur salts.

18. A clear amber yellow coumarone resin on destructive distillationields greater t an 85% by weight of disti lates, and furthercharacterized by the fact that films thereof will not turn milky whensubmerged in water. 19. Those steps in the process of producing a lightcolored resin from oils containing compounds of the coumarone-indenegroup together with dark resin-formin bodies, "which consist in sotreating the 01 with sulphuric acid as to lymerize the darkresin-forming bodies without substantial polymerization of the lightresin-forming coumarone-indene compoundgand separating the polymerizeddark resin-forming bodies from the oil containing the unpolymerizedlight resin-forming compounds.

20. Those steps in the process of producing a light colored resin fromoils containing compounds of the coumarone-indene with darkresin-forming bodies, which consist in so treating the oil withsulphuric acid as to polymerize the dark resin-forming bodies withoutsubstantial polymerization of the light resin-forming coumarone-indenecompounds, and distilling the oil so as to separate the polymerized darkresin-forming bodies from the oil containing the unpolymerizcd lightresin-forming compounds.

21. Those steps inthe process of producing a light colored resin fromoils containing compounds of the eoumarone-indene group together withdark reeinforming bodies, which consist in polymerizing the darkresin-forming bodies without substan tial polymerization of the lightresin-forniing coumarone-indene compounds, and separating thepolymerized dark resin-forming bodies from the oil containing theunpolymerized light resin-forming compounds.

22. Those steps in the process of producing a light colored resin fromoils containing compounds of the coumarone-indene group together withdark resin-forming bodies, which consist in polymerizing the darkresin-forming bodies without substantial polymerization of the lightresin-forming eoumarone-indene compounds, and distilling the oil so asto separate the polymerized dark resin forming bodies from the oilcontaining the unpolymerized light resin-forming compounds.

23. Those steps in the process of producing a light colored resin fromoils containing compounds of the eoumarone-indene group together withdark resin-forming bodies, which consist in converting into separableform the dark resin-forming bodies which would would otherwise impart adark color to the resin, separating si'ieh bodies from the oil, andthereafter polymerizing the light resin-forming eoiunarone-indenecompounds.

24. Those steps in the process of producimpart a dark iug a lightcolored resin from oils containing compounds of the coumarouc-indeuegroup together with dark resin-forming bodies, which consist inconri-rting into soparable form the dark resin-forming bodies whichwould otherwise impart a dark color to the resin, and separating sin-hbodies from the oil.

25. Those steps in the process of produc ing a light colored resin fromoils containin; compounds of the rouniarone-indcne group together withbodies which would color to the resin, which consist in converting intoseparable form the bodicswhich would otherwise impart the dark color tothe resin, separating such bodies from the oil by distillation, andthereafter subjecting the distillate to a polymerizing treatment topolymerize the light resin-forming couniarone-indcne compounds.

26. Those steps in the process of producing a light colored resin fromoils containing compounds of the coumarone-indene group together withbodies which would otherwise impartv a dark color to the resin, whichconsist in removing such bodies from the oil by treatment with sulphuricacid followed by distillation, and thereafter poly: lnetizing the lightresin-forming eoumaroneindcne compounds.

In testimony that I claim the foregoing I have hereunto set my hand.

HARRY CLIFFORD KARNS.

\Vitnesses Grmmrr C. CLARK,

W. G. LODGE.

(ill

oil containing the unpolymerizcd light resin-forming compounds.

21. These steps in the process of producing a light colored resin fromoils containing compounds of the coumarone-indene group together withdark resin-forming bodies, which consist in polymerizing the darkresin-forming bodies without substantial polymerization of the lightresin-torus ing coumarone-indene compounds, and separating thepolymerized dark resin-forming bodies from the oil containing theunpolymerized light resin-forming compounds.

22. Those steps in the process of producing a light colored resin fromoils containing compounds of the coumarone-indene group together withdark resin-forming bodies, which consist in polymerizing the darkresin-forming bodies without substantial polymerization of the lightresin-forming coumarone-indene compounds, and distilling the oil so asto separate the polymerized dark resin-forming bodies from the oilcontaining the unpolymcrized light resin-forming compounds.

23. Those steps in the process of producing a. light colored resin fromoils containing compounds of the coumnrone-indene group together withdark resin-forming bodies, which consist in converting into separableform the dark resin-forming bodies which would would otherwise impgirt adark color to the resin, separating such bodies from the oil, andthereafter polymerizing the light resin-forming cou narone-indene comunds.

24. Those steps in the process of producing a light colored resin fromoils containing compounds of the coumaroneindcne group together withdark resind'orming bodies, which consist in conn rting into separableform the dark resin-forming bodies which would otherwise impart a darkcolor to the resin, and separating such bodies from the oil.

25. Those steps in the process of producing a. light colored resin fromoils containing compounds of the eoiunarone-indeue group together withbodies which would impart 21 dark color to the resin. which consist inconverting into separable form the bodieswhich would otherwise impartthe dark color to the resin, separating such bodies from the oil bydistillation, and thereafter subjecting the distillate to a polymerizingtreatment to polymerize the light resin-forn'iing coumaronc-indenecompounds.

26. Those steps in the process of producing a light colored resin fromoils containing compounds of the coulmu-ouc-indene group together withbodies which would otherwise impart a dark color to the resin, whichconsist in removing such bodies from the oil by treatment with sulphuricacid followed by distillation, and thereafter polymerizing the lightresin-forming coumaroneindenc compounds.

In testimony that I claim the foregoing I have hereunto set my hand.

HARRY CLIFFORD KAIlNS.

\Vitnesses (irrnnnn'r C. CLARK,

W. G. Loner.

, Certificate of Correction.

It is hereby certified that in Letters Patent No. 1,541,226, grantedJune 9, 1925,

upon the application of I-Ierry Cliflord ,Karnis, of Philadelphia,Pennsylvania. for

an -m rovement in Coumarone-Indene Resins and Processes of Making theSame, an error appears in the printed specification requiring correctionas follows:

Page

2, line 48, strike out the formula and insert instead (0,,,,,H,,,,,,0),:and

that the said Letters Patent should be .read with this correctiontherein that the some ma conform to the record of the case in the PatentOflice.

Signed and sealed this 21st day of July, A. D. 1925.

KARL FENNING, Acting Commissioner of Patents.

(iii

Certificate of Correction.

It is hereby certified that in Letters Patent No. 1,541,226, grantedJune 9, 1925, upon the application of Harry Clifford jKarn s, ofPhiladelphia. Pennsvlvanie; for an improvement in Coumerone-IndeneResins and Pmcesses of Making the Same, an error appears in the printedspecification requiring correction as follows: Page 2, line 48, strikeout the formula. and insert instead (G H Q and that the said LettersPatent should be read with this correction therein that the same maconform to the record of the case in the Patent Oflice.

Sign and sealed tnis 21st day of July, A. D. 1925.

[m] KARL FENNING,

Acting Commissioner of Patents.

